EP0783880B1 - Matériau composite durcissable par la lumière - Google Patents

Matériau composite durcissable par la lumière Download PDF

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Publication number
EP0783880B1
EP0783880B1 EP96250293A EP96250293A EP0783880B1 EP 0783880 B1 EP0783880 B1 EP 0783880B1 EP 96250293 A EP96250293 A EP 96250293A EP 96250293 A EP96250293 A EP 96250293A EP 0783880 B1 EP0783880 B1 EP 0783880B1
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Prior art keywords
composite material
material according
dental
radicals
light
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EP96250293A
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German (de)
English (en)
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EP0783880A3 (fr
EP0783880A2 (fr
Inventor
Norbert Prof. Dr. Moszner
Volker Dr. Rheinberger
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Ivoclar Vivadent AG
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Ivoclar Vivadent AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to a light-curing composite material, which due to a content of special polymerization inhibitors a reduced sensitivity to light and a improved stability against premature polymerization when venting, e.g. by applying negative pressure. Further The invention also relates to the use of the composite material as well as shaped dental products.
  • Light-curing composite materials are compositions that in addition to light-curing monomers, fillers and possibly other Contain additives.
  • Used in the dental field light-curing composite materials are one-component systems, characterized by rapid curing due to polymerization, good storage stability, little discoloration due to the used polymerization initiator system and a very low Mark porosity after curing.
  • the cold-curing composite materials become the light-curing Composites in the dental field, especially as filling composites or Cements used widely (see P. Riethe, caries prophylaxis and conservative therapy in "Color Atlas of Dentistry” Volume 6, page 190, G. Thieme Verlag, Stuttgart-New York 1994).
  • For the stabilization of light-curable dental filling composites i.e.
  • stabilizers especially substituted phenols, e.g. 2,6-di-tert-butyl-4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ) (see J. Viohl et al., The chemistry of dental Filling plastics, C. Hanser Verlag, Kunststoff-Vienna 1986, page 27).
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • MEHQ hydroquinone monomethyl ether
  • a disadvantage of the known light-curing dental composite materials and in particular of the so-called hybrid composite materials is, however, that their handling, e.g. in the form of commonly used pastes, can lead to undesired premature curing as a result of intensive lighting or sunlight (cf. P. Dionysopoulos , DC Watts, J. Oral Rehabil. 17 (1990) 9). Accordingly, the international standard for composite dental filling materials (ISO 4049: 1988) requires that they should be stable for at least 60 seconds at an illuminance of approx. 10000 lx, ie they should not harden.
  • the photosensitivity of a dental composite material is conventionally adjusted by suitable coordination of the composition and concentration of the photoinitiator used and by a targeted selection of the filler components used.
  • a reduction in light sensitivity by increasing the concentration of the stabilizers used does not usually lead to the goal. This is probably because the phenolic compounds usually used as stabilizers, such as MEHQ, are so-called aerobic stabilizers which are only effective in conjunction with oxygen dissolved in the composite material and thereby the growth of the polymer radicals via peroxy radicals formed with the oxygen inhibit (cf. JJ Kurland, J. Polym. Sci., Polym. Chem. Ed. 18 (1980) 1139).
  • anaerobic stabilizer In addition to the conventional aerobic stabilizers, substances are also known which can effectively inhibit the radical vinyl polymerization even in the absence of oxygen and are therefore also referred to as anaerobic stabilizers.
  • Such an anaerobic stabilizer is, for example, phenothiazine, which, in contrast to MEHQ, can inhibit the polymerization of acrylic acid even in the absence of oxygen (cf. LB Levy, J. Polym. Sci., Part A, Polym. Chem. 30 (1992) 569) ,
  • so-called stable organic radicals are also described in the literature, which can be used as polymerization inhibitors.
  • DPPH 2,2-diphenyl-1-picrylhydrazyl
  • galvinoxyl triphenylmethyl
  • 2,2,6,6-tetramethylpiperidinyl-1-oxyl radical cf. ES Gould, Mechanism and Structure in Organic Chemistry, Verlag Chemie, Weinheim, 1962, p. 816.
  • US Pat. No. 4,839,401 discloses light-curable fissure sealants, the 2,2-propane-bis [3- (4-phenoxy) -1,2-dihydroxypropane-1-methacrylate] and triethylene glycol dimethacrylate in a weight ratio from 55:45, a polymerization initiator, Titanium dioxide and diethylaminoethyl methacrylate (DEA-EMA) as a polymerization accelerator contain.
  • the fissure sealants can contain up to 50% filler.
  • the DEA-EMA preferably contains 50 to 100 ppm phenothiazine.
  • organic radicals are very effective free radical scavengers to be expected that their incorporation into composite materials a only causes incomplete curing, which would be very disadvantageous since this causes a significant deterioration in the mechanical properties of the cured material would go hand in hand.
  • the invention is accordingly based on the object of a light-curing To provide composite material which polymerized prematurely when venting and its sensitivity to light is set in such a way that a by Daylight-induced polymerization is inhibited, however induced by light in the wavelength range of 400-550 nm Polymerization is not hindered and therefore a significant deterioration the mechanical properties of the cured Composite material is avoided.
  • the invention also relates to the use of the composite material according to claims 10 and 11 and the shaped dental product according to claims 12 and 13th
  • the light-curing composite material according to the invention is thereby characterized in that it is (a) at least one light-curing monomer, (b) at least one filler and (c) at least one anaerobic stabilizer and / or stable organic radicals contains and is curable with light in the wavelength range from 400 to 550 nm.
  • Anaerobic stabilizers are compounds that are radical Vinyl polymerization even in the absence of oxygen can inhibit. These are anaerobic stabilizers in an amount of 0.001 to 1.0, especially 0.001 to 0.50 and particularly preferably 0.001 to 0.20% by weight in the invention Composite material included.
  • stable organic radicals are among stable organic radicals to understand such organic radicals that are at room temperature in the solid state or in solution a half-life of at least 30 days, in particular of at least 12 months.
  • the radical stability is known to be (see H.A. Staab, Introduction to Theoretical Organic Chemistry, Verlag Chemie, Weinheim 1966, pp. 442 ff.) Mainly through the stabilization of mesomerism of the radicals or the destabilization of the corresponding dimeric combination products by steric Effects.
  • stable carbon radicals such as tribiphenylmethyl
  • stable oxygen radicals such as Galvinoxyl
  • stable nitrogen radicals such as DPPH radicals
  • the stable organic radicals are in one Amount of 0.001 to 1.0, especially 0.001 to 0.50 and especially preferably 0.001 to 0.20% by weight in the invention Composite material included.
  • the contains Composite material according to the invention preferably also conventional Polymerization inhibitors.
  • Polymerization inhibitors are 2,6-di-tert-butyl-4-methylphenol (BHT) and hydroquinone monomethyl ether (MEHQ).
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • MEHQ hydroquinone monomethyl ether
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • MEHQ hydroquinone monomethyl ether
  • the composite material according to the invention also contains at least a light-curing monomer.
  • Preferred examples of these are methyl (meth) acrylate, Isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, Tetraethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Decanediol di (meth) acrylate, Dodecanediol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate
  • Triethylene glycol di (meth) acrylate are particularly preferred, 2,2-bis-4- (3-methacryloxy-2-hydroxypropoxy) phenylpropane (Bis-GMA) and that by reacting 1 mole 2,2,4-trimethylhexamethylene diisocyanate with 2 moles of 2-hydroxyethyl methacrylate received products.
  • the total amount of light-curing monomers is preferably in the composite material 7 to 80 according to the invention, particularly preferred 14 to 50% by weight.
  • the composite material according to the invention further contains at least one filler.
  • Particularly suitable fillers are inorganic fillers and in particular quartz or glass ceramic powder, aluminum oxides, mixed oxides, such as SiO 2 -ZrO 2 mixed oxide, or radiopaque fillers, such as ytterbium trifluoride.
  • Particularly preferred fillers are glass powder, for example barium glass, barium silicate glass, lithium or aluminum silicate glass powder and finely divided silicas, such as pyrogenic or precipitated silicas.
  • the fillers are preferably used in an amount of 10 to 90, in particular 48 to 85% by weight in the composite material according to the invention used.
  • the composite material preferably also contains initiators for photopolymerization, e.g. benzophenone, Benzoin or derivatives of these.
  • Preferred photoinitiators are the ⁇ -diketones such as 9,10-phenanthrenequinone, diacetyl, furil, Anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil.
  • camphorquinone is preferably used.
  • the photoinitiators in combination with an amine as an activator used e.g. N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine and especially N- (2-cyanoethyl) -N-methylaniline come into question.
  • the composite material according to the invention can also usual additives and especially for dental composite materials usual additives, such as dyes, pigments, plasticizers, lubricants, Contain rheology modifiers or UV stabilizers.
  • additives such as dyes, pigments, plasticizers, lubricants, Contain rheology modifiers or UV stabilizers.
  • the invention required stabilizers, namely the anaerobic stabilizer and / or the stable organic radicals, to any one Point in time during the manufacturing process e.g. by simple Mixing can be incorporated into the composite material.
  • the composite material according to the invention is particularly distinguished characterized in that its photosensitivity by content of small amounts of anaerobic stabilizer and / or stable organic radicals is set so that it is neither Venting, e.g. by applying a vacuum, even with exposure Polymerized prematurely using daylight. Both can the vacuum stability as well as the light sensitivity simple by the type and amount of anaerobic stabilizer and / or stable organic radicals can be controlled.
  • the composite material according to the invention Particularly suitable as a dental filling material.
  • the invention also relates to the use of the composite material as dental material and in particular the use of the anaerobic stabilizer and / or the stable organic radicals to reduce the sensitivity of the dental material to light and to inhibit premature polymerization of the dental material when venting.
  • the invention also relates to one from the invention Dental material shaped composite material, in particular a filling, a crown or a bridge, which is the composite material contains in at least partially hardened form. The deformation of the composite material takes place in itself known way.
  • the monomer mixture had the following composition: component Wt .-% Bis-GMA 41,77 UDMA 37.42 TEGDMA 20.00 MEHQ 0.01 CC 0.30 CEMA 0.50
  • This monomer mixture was then mixed with fillers to produce a composite material of the following composition: Wt .-% component 26.0 monomer 44.0 silanized barium aluminum silicate glass (glass filler, Schott glass works) 14.5 Ytterbium trifluoride (Rhone-Poulenc) 14.5 silanized spherical SiO 2 -ZrO 2 mixed oxide (spherosil, Tokyamo Soda) 1.0 Titanized fumed silica (Ox-50, Degussa)
  • phenothiazine as anaerobic stabilizer or 2,2,6,6-tetramethylpiperidinyl-1-oxyl radicals (TEMPO) or 2,2-diphenyl-1-picrylhydrazyl radicals (DPPH) as stable organic radicals were then added to this composite material .
  • the stated amounts relate to the amount of composite material used without phenothiazine, TEMPO and DPPH.
  • the light sensitivity, the flexural strength and the flexural modulus were then determined according to ISO 4049. The measured values are listed below.
  • Example 1 A composite material of the following composition was produced as in Example 1: Wt .-% component 19.0 Monomer mixture according to example 1 51.0 silanized barium aluminum silicate glass (glass filler) 14.5 ytterbiumtrifluoride 14.5 silanized spherical SiO 2 -ZrO 2 mixed oxide (spherosil) 1.0 silanized pyrogenic silica (Ox-50)
  • the paste obtained was deaerated in the kneader at ⁇ 50 mbar.
  • the paste started after about 5 minutes. to polymerize.
  • a paste of the same composition but with an additive 0.06% by weight of phenothiazine (based on the amount of the paste before addition of phenothiazine) was 20 min. long stable, what a complete venting is sufficient.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Dental Prosthetics (AREA)
  • Reinforced Plastic Materials (AREA)

Claims (13)

  1. Matériau composite photodurcissable, caractérisé en ce qu'il contient
    (a) au moins un monomère photodurcissable,
    (b) au moins une matière de charge, et
    (c) au moins un agent stabilisant anaérobie en une quantité de 0,001 à 1,0% en poids et/ou des radicaux organiques stables,
    et en ce qu'il peut être durci par de la lumière dans la plage de longueur d'onde de 400 à 550 nm.
  2. Matériau composite selon la revendication 1, caractérisé en ce qu'il contient comme agent stabilisant anaérobie de la phénothiazine et/ou un dérivé de celle-ci de la formule 1 :
    Figure 00230001
    dans laquelle R, R1, X, Y, R2, R3, R4, R5, R6 et R7 ont indépendamment les uns des autres les significations suivantes :
    R et R1 =
    alkylène ou oxyalkylène en C1 à C5 ou arylène en C6 à C12,
    X et Y =
    H, halogène, NO2, NH2, NR2R3, OH, OR4, CN, CHO, CO-R5, COOH, CO-NH2, CO-OR6, CH2=CH-, CH2=CH-CO-, CH2=C(CH3)-CO-, SH ou S-R7,
    R2 à R7 =
    alkyle, alcényle, aryle, alkylaryle ou arylalkyle possédant chacun de 1 à 12 atomes de carbone.
  3. Matériau composite selon la revendication 1 ou la revendication 2, caractérisé en ce qu'il contient en particulier de 0,001 à 0,50% en poids et de façon particulièrement préférée de 0,001 à 0,20% en poids d'agent stabilisant anaérobie.
  4. Matériau composite selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient comme radicaux organiques stables des radicaux 2,2-diphényl-1-picrylhydrazyle (DPPH), galvinoxyle, triphénylméthyle et/ou des radicaux des formules II et III, en particulier des radicaux 2,2,6,6-tétraméthylpipéridinyl-1-oxyle :
    Figure 00240001
    dans lesquelles X, Y, Z, W et R ont indépendamment les uns des autres les significations suivantes :
    X =
    O ou S,
    Y et Z =
    O, S ou absents,
    W =
    C ou absent,
    R =
    H ou alkyle, alcényle, aryle, alkylaryle ou arylalkyle possédant chacun de 1 à 12 atomes de carbone.
  5. Matériau composite selon l'une des revendications 1 à 4, caractérisé en ce qu'il contient de 0,001 à 1,0% en poids, en particulier de 0,001 à 0,50% en poids et de façon particulièrement préférée de 0,001 à 0,20% en poids de radicaux organiques stables.
  6. Matériau composite selon l'une des revendications 1 à 5, caractérisé en ce qu'il contient des inhibiteurs de polymérisation classique, notamment en une quantité allant jusqu'à 1,0% en poids.
  7. Matériau composite selon l'une des revendications 1 à 6, caractérisé en ce qu'il contient de 7 à 80% en poids et en particulier de 14 à 50% en poids de monomères photodurcissables (a).
  8. Matériau composite selon l'une des revendications 1 à 7, caractérisé en ce qu'il contient de 10 à 90% en poids et en particulier de 48 à 85% en poids de matières de charge (b).
  9. Matériau composite selon l'une des revendications 1 à 8, caractérisé en ce qu'il s'agit d'un matériau pour des couronnes ou des bridges et en particulier d'un matériau d'obturation.
  10. Utilisation du matériau composite selon l'une des revendications 1 à 9 à titre de matériau dentaire.
  11. Utilisation selon la revendication 1, dans laquelle l'agent stabilisant anaérobie et/ou les radicaux organiques stables sont utilisés pour réduire la sensibilité à la lumière du matériau dentaire et pour inhiber la polymérisation prématurée du matériau dentaire lors du dégazage.
  12. Produit dentaire formé, caractérisé en ce qu'il contient le matériau composite selon l'une des revendications 1 à 9 sous une forme durcie au moins en partie.
  13. Produit dentaire selon la revendication 12, caractérisé en ce qu'il s'agit d'une obturation, d'une couronne ou d'un bridge.
EP96250293A 1996-01-12 1996-12-18 Matériau composite durcissable par la lumière Revoked EP0783880B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19601924 1996-01-12
DE19601924A DE19601924B4 (de) 1996-01-12 1996-01-12 Stabile organische Radikale enthaltendes, lichthärtendes Kompositmaterial und dessen Verwendung sowie die Verwendung eines stabilen organischen Radikals zur Herstellung eines Dentalmaterials

Publications (3)

Publication Number Publication Date
EP0783880A2 EP0783880A2 (fr) 1997-07-16
EP0783880A3 EP0783880A3 (fr) 2000-05-17
EP0783880B1 true EP0783880B1 (fr) 2004-08-18

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Country Status (7)

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US (2) US5847025A (fr)
EP (1) EP0783880B1 (fr)
JP (1) JP3021378B2 (fr)
AT (1) ATE273683T1 (fr)
AU (1) AU697885B2 (fr)
CA (1) CA2194533C (fr)
DE (2) DE19601924B4 (fr)

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EP2374445A2 (fr) 2010-04-12 2011-10-12 VOCO GmbH Composition dentaire multicomposant à durcissement double
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DE102010003883A1 (de) 2010-04-12 2011-10-13 Voco Gmbh Lichthärtbares Kompositmaterial
EP2436363A2 (fr) 2010-09-30 2012-04-04 VOCO GmbH Composition comprenant un monomère doté d'un élément structurel polyalicyclique destiné à remplir et/ou sceller un canal radiculaire
EP2436366A2 (fr) 2010-09-30 2012-04-04 VOCO GmbH Matériau composite comprenant un monomère doté d'une structure polyalicyclique comme matériau de scellement
EP2436668A1 (fr) 2010-09-30 2012-04-04 VOCO GmbH Composés polymérisables comprenant un élément structurel polyalicyclique
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EP2481391A2 (fr) 2011-01-27 2012-08-01 VOCO GmbH Superstructures dentaires provisoires ainsi que matériaux utilisés pour leur fabrication et procédé correspondant
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EP3011949A1 (fr) 2014-10-23 2016-04-27 VOCO GmbH Materiau dentaire durcissable
DE102014116389A1 (de) 2014-11-11 2016-05-12 Voco Gmbh Radikalisch härtbare dentale Zusammensetzungen
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EP3782599A1 (fr) 2019-08-19 2021-02-24 VOCO GmbH Composition dentaire polymérisable à base de silanes condensés
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EP2374444A2 (fr) 2010-04-12 2011-10-12 VOCO GmbH Masse de recouvrement dentaire
DE102010003881A1 (de) 2010-04-12 2011-10-13 Voco Gmbh Dentale Abdeckmasse
DE102010003884A1 (de) 2010-04-12 2011-10-13 Voco Gmbh Dualhärtende, mehrkomponentige dentale Zusammensetzung
DE102010003883A1 (de) 2010-04-12 2011-10-13 Voco Gmbh Lichthärtbares Kompositmaterial
EP2436363A2 (fr) 2010-09-30 2012-04-04 VOCO GmbH Composition comprenant un monomère doté d'un élément structurel polyalicyclique destiné à remplir et/ou sceller un canal radiculaire
EP2436366A2 (fr) 2010-09-30 2012-04-04 VOCO GmbH Matériau composite comprenant un monomère doté d'une structure polyalicyclique comme matériau de scellement
EP2436668A1 (fr) 2010-09-30 2012-04-04 VOCO GmbH Composés polymérisables comprenant un élément structurel polyalicyclique
EP2436364A2 (fr) 2010-09-30 2012-04-04 VOCO GmbH Composition de laque comprenant un monomère doté d'un élément structurel polyalicyclique
EP2436365A2 (fr) 2010-09-30 2012-04-04 VOCO GmbH Matériau composite comprenant un monomère doté d'un élément structurel polyalicyclique
US8915736B2 (en) 2010-09-30 2014-12-23 Voco Gmbh Composition comprising a monomer with a polyalicyclic structure element for filling and/or sealing a root canal
EP2450025A1 (fr) 2010-11-08 2012-05-09 VOCO GmbH Dérivés d'acide phosphorique polymérisables comprenant un élément structurel polyalicyclique
DE102011003289A1 (de) 2011-01-27 2012-08-02 Voco Gmbh Dentale provisorische Suprakonstruktionen sowie Materialien zu ihrer Herstellung und entsprechende Verfahren
EP2481391A2 (fr) 2011-01-27 2012-08-01 VOCO GmbH Superstructures dentaires provisoires ainsi que matériaux utilisés pour leur fabrication et procédé correspondant
EP2578200A1 (fr) 2011-10-04 2013-04-10 VOCO GmbH Compositions pour l'infiltration et/ou le scellement de la matière dentaire dure et procédé correspondant
EP2623086A2 (fr) 2012-02-02 2013-08-07 VOCO GmbH Mélange durcissable comprenant un plastifiant avec un élément structurel polyalicyclique destiné à être utilisé dans la fabrication de matériaux dentaires
EP2623087A2 (fr) 2012-02-02 2013-08-07 VOCO GmbH Matériaux composites dentaires contenant des plastifiants tricycliques
DE102012001979A1 (de) 2012-02-02 2013-08-08 Voco Gmbh Härtbares Gemisch umfassend Weichmacher mit einem polyalicyclischen Strukturelement zur Anwendung bei der Herstellung dentaler Werkstoffe
DE102012001978A1 (de) 2012-02-02 2013-08-08 Voco Gmbh Dentale Kompositmaterialien enthaltend tricyclische Weichmacher
EP2698142A2 (fr) 2012-08-15 2014-02-19 VOCO GmbH Matériaux de obturation dentaire et laque dentaire destinés à empêcher la formation de biofilm de Streptococcus mutans et leur fabrication
DE102012214540A1 (de) 2012-08-15 2014-02-20 Helmholtz-Zentrum für Infektionsforschung GmbH Zahnfüllungsmaterialien und Zahnlacke zur Hemmung der Biofilmbildung von Streptococcus mutans und deren Herstellung
EP2716276A2 (fr) 2012-10-05 2014-04-09 VOCO GmbH Kit et procédé de fabrication indirecte d'inlays composites
US9833387B2 (en) 2012-10-05 2017-12-05 Voco Gmbh Kit and method for indirect chairside production of composite inlays
EP2952516A1 (fr) 2014-06-03 2015-12-09 VOCO GmbH Liaison de polysiloxane et matériaux dentaires ainsi fabriqués
DE102014210432A1 (de) 2014-06-03 2015-12-03 Voco Gmbh Polysiloxanverbindung und daraus herstellbare Dentalmaterialien
EP3011949A1 (fr) 2014-10-23 2016-04-27 VOCO GmbH Materiau dentaire durcissable
DE102015220373A1 (de) 2014-10-23 2016-04-28 Voco Gmbh Härtbares Dentalmaterial
US9839585B2 (en) 2014-11-11 2017-12-12 Voco Gmbh Free radically curable dental compositions
EP3020360A1 (fr) 2014-11-11 2016-05-18 VOCO GmbH Compositions dentaires à durcissement radicalaire
EP3020361A1 (fr) 2014-11-11 2016-05-18 VOCO GmbH Utilisation de compositions a durcissement radicalaire dans un procede de fabrication generative
US9795541B2 (en) 2014-11-11 2017-10-24 Voco Gmbh Use of free radically curable compositions in additive manufacturing methods
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AU697885B2 (en) 1998-10-22
DE19601924B4 (de) 2005-01-13
ATE273683T1 (de) 2004-09-15
AU1004197A (en) 1997-08-14
CA2194533A1 (fr) 1997-07-13
EP0783880A3 (fr) 2000-05-17
JP3021378B2 (ja) 2000-03-15
US5985958A (en) 1999-11-16
EP0783880A2 (fr) 1997-07-16
DE19601924A1 (de) 1997-07-17
JPH09194515A (ja) 1997-07-29
US5847025A (en) 1998-12-08
DE59611061D1 (de) 2004-09-23
CA2194533C (fr) 2002-05-14

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